Synthesis of a Remarkably Stable Dehydro[14]annulene

Palmer, Grant J.; Parkin, Sean; Anthony, John E.

doi:10.1002/1521-3773(20010702)40:13<2509::aid-anie2509>3.0.co;2-f

Cited by 22 publications

(7 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It is noteworthy that 11 was remarkably stable under ambient conditions and showed no reactivity towards the intramolecular cyclization of the two butadiyne units, unlike 14 19. Anthony and co‐workers also observed similar stabilities for 15 and 16 18. Our results likely support their hypothesis that the distance between the two butadiyne units is less important to the stability than the degree of conjugation along the macrocyclic π circuit.…”

Section: Chlorination Of β‐Haloporphyrins 1 With Palau’chlorsupporting

confidence: 84%

“…The two butadiyne units were not linear and were distorted to take an elliptic conformation, in which the transannular distances between the central carbon atoms (C22‐C24 and C22′‐C24′) were elongated by 0.67–0.69 Å relative to those of the edge (C5‐C7 and C5′‐C7′). The central stretch was larger than that of the acenaphthylene derivative 15 (0.63 Å),18 thus indicating the large structural distortion in 11 . On the other hand, the C22‐C24 (C22′‐C24′) distance of 11 (3.20 Å) was comparable to those in naphthalene derivative 14 (ca.…”

Section: Chlorination Of β‐Haloporphyrins 1 With Palau’chlormentioning

confidence: 93%

“…3.18 Å), acenaphthylene derivative 15 (3.23 Å from X‐ray diffraction analysis), and fluoranthene derivative 16 (ca. 3.25 Å) 18. It is noteworthy that 11 was remarkably stable under ambient conditions and showed no reactivity towards the intramolecular cyclization of the two butadiyne units, unlike 14 19.…”

Section: Chlorination Of β‐Haloporphyrins 1 With Palau’chlormentioning

confidence: 96%

See 2 more Smart Citations

meso,β‐Oligohaloporphyrins as Useful Synthetic Intermediates of Diphenylamine‐Fused Porphyrin and meso‐to‐meso β‐to‐β Doubly Butadiyne‐Bridged Diporphyrin

2015

View full text Add to dashboard Cite

The chlorination of b-halo or b,b-dihaloporphyrins with 2-chloro-1,3-bis(methoxycarbonyl)guanidine (Palau' Chlor) proceeded selectively at the neighboring unsubstituted meso position to affordmeso,b-dihalo or meso,b,b-trihaloporphyrins.S ucho ligohaloporphyrins are useful platforms for constructing more-elaborate porphyrin-based extended p systems.F or example,m eso-chloro-b,b-diiodoporphyrin participated in an efficient single-step synthesis of ad iphenylaminefused porphyrin. In addition, meso-chloro-b-iodoporphyrin was transformed in stepwise fashion into an efficiently conjugated meso-to-meso,b-to-b doubly butadiyne-linked porphyrin dimer,asystem which was previously difficult to access without such haloporphyrin precursors.Porphyrins are an important class of arenes in light of the wide range of applications that arise from their intriguing electronic and optical properties.[1] Peripheral functionalizations of porphyrins have attracted considerable attention since they allow the creation of av ariety of porphyrin-based functional materials.[2] In these recent studies,haloporphyrins play an important role as indispensable synthetic intermediates in reactions such as cross-coupling reactions, [3] aromatic nucleophilic substitution (S N Ar) reactions, [4] and peripheral metalations.[5] Therefore,d evelopment of an ew class of haloporphyrin intermediates should lead to an increase in the number of usable synthetic strategies and hence easier access to desirable porphyrin derivatives.Thee lectrophilic halogenation of porphyrins usually occurs selectively at their electron-rich meso positions to afford meso-haloporphyrins.[6] As ac omplementary method, we recently reported the facile preparation of meso-free bhaloporphyrins and b,b-dihaloporphyrins by Cu-mediated halogenation of b-borylporphyrins. [7, 8] These b-haloporphyrins allowed the synthesis of various functional porphyrins that were difficult to access without such precursors.[5d, 8] Herein, we disclose an efficient synthetic route to oligohaloporphyrins that bear more than two halogen substituents at the meso and neighboring b positions.T ot he best of our knowledge,t he efficient synthesis of such synthetic platforms has yet to be reported in the literature. [9] We thought that meso-free b-haloporphyrins were attractive precursors of meso,b-oligohaloporphyrins because of the presence of the reactive meso position. Attempted halogenation reactions of b-chloro Ni II porphyrin 1a with various halogenating reagents were carried out (see Table S1 in the Supporting Information). Bromination with N-bromosuccinimide (NBS) [6a] or iodination with ac ombination of I 2 and [bis(trifluoroacetoxy)iodo]benzene [6b] afforded the corresponding b-halo-b-chloroporphyrins 3 as unwanted side products.O nt he other hand, we found that both PhICl 2 [6c, 10] and 2-chloro-1,3-bis(methoxycarbonyl)guanidine (Palau' Chlor) [11] were efficient chlorinating reagents to provide meso,b-dichloroporphyrin 2aCl.C hen and co-workers reported that PhICl 2 was not suitable f...

show abstract

Section: Chlorination Of β‐Haloporphyrins 1 With Palau’chlorsupporting

confidence: 84%

Section: Chlorination Of β‐Haloporphyrins 1 With Palau’chlormentioning

confidence: 93%

Section: Chlorination Of β‐Haloporphyrins 1 With Palau’chlormentioning

confidence: 96%

See 1 more Smart Citation

meso,β‐Oligohaloporphyrins as Useful Synthetic Intermediates of Diphenylamine‐Fused Porphyrin and meso‐to‐meso β‐to‐β Doubly Butadiyne‐Bridged Diporphyrin

2015

View full text Add to dashboard Cite

show abstract

“…The acetylene units of 1 are almost linear with bending angles of less than 5º and the π-conjugated backbone is distinctly planar. The transannular interatomic distance between the sp carbons of 1 is 2.80 Å, which is slightly longer than that of dibenzocyclooctadienediyne (2.61 Å) [16] but shorter than that of a octadehydrodiacenaphtho [14]annulene derivative (2.97 Å) [17]. The observed short interatomic distance of 1 provides an indication for possible transannular C-C bond formation.…”

Section: Magnetic and Structural Properties Of Tetradehydrodinaphtho[mentioning

confidence: 92%

Tetradehydrodinaphtho[10]annulene and its transformation into zethrene: A hitherto unknown dehydroannulene and a forgotten aromatic hydrocarbon

Umeda

Hibi

Miki

et al. 2010

Pure and Applied Chemistry

View full text Add to dashboard Cite

The synthesis and structural characterization of a hitherto unknown tetradehydrodinaphtho[10]annulene, which had eluded isolation since attempts initiated during the late 1960s, was achieved. Moreover, the dehydroannulene was transformed into stable derivatives of zethrene, which was first reported in 1955, but forgotten for a long time. These molecules are substituted at the 7,14-positions and open the door to the zethrene family for potential application as optoelectronic materials.

show abstract

“…Palmer et al [184] prepared a stable dehydro [14]annulene by reaction of a 1-silyl-2-stannylethyne and a bromoaromatic functionality. Lukevics et al [185] synthesized unsymmetrical diynes by reactions between alkynylstannanes and terminal bromoalkynes.…”

Section: Couplings Of Alkynyltinsmentioning

confidence: 99%

Organotin Reagents in Cross‐Coupling Reactions

Martín‐Matute

Szabó

Mitchell

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

View full text Add to dashboard Cite

Synthesis of a Remarkably Stable Dehydro[14]annulene

Abstract: The substituents at the peri positions of dehydro[14]annulenes 1 have a dramatic effect on the stability of these macrocycles, and lead to derivatives that are stable even at elevated temperatures (up to 190°C).

Cited by 22 publications

References 24 publications

meso,β‐Oligohaloporphyrins as Useful Synthetic Intermediates of Diphenylamine‐Fused Porphyrin and meso‐to‐meso β‐to‐β Doubly Butadiyne‐Bridged Diporphyrin

meso,β‐Oligohaloporphyrins as Useful Synthetic Intermediates of Diphenylamine‐Fused Porphyrin and meso‐to‐meso β‐to‐β Doubly Butadiyne‐Bridged Diporphyrin

Tetradehydrodinaphtho[10]annulene and its transformation into zethrene: A hitherto unknown dehydroannulene and a forgotten aromatic hydrocarbon

Organotin Reagents in Cross‐Coupling Reactions

Contact Info

Product

Resources

About